CN106746621A - Unleaded fluogermanate glass of High Temperature Optical sensing material erbium and ytterbium codoping and preparation method thereof - Google Patents
Unleaded fluogermanate glass of High Temperature Optical sensing material erbium and ytterbium codoping and preparation method thereof Download PDFInfo
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- CN106746621A CN106746621A CN201611115573.4A CN201611115573A CN106746621A CN 106746621 A CN106746621 A CN 106746621A CN 201611115573 A CN201611115573 A CN 201611115573A CN 106746621 A CN106746621 A CN 106746621A
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C4/00—Compositions for glass with special properties
- C03C4/04—Compositions for glass with special properties for photosensitive glass
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/12—Silica-free oxide glass compositions
- C03C3/253—Silica-free oxide glass compositions containing germanium
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
- C09K11/7775—Germanates
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Abstract
The invention discloses a kind of unleaded fluogermanate glass of High Temperature Optical sensing material erbium and ytterbium codoping, by to addition erbium ytterbium ion in fluogermanate glass, erbium ytterbium ion can be realized highly doped in fluogermanate glass, can further improve pump energy utilization rate and luminous efficiency, highly sensitive TEMP is capable of achieving in shorter optical fiber, the practicality of temperature sensor is improve.Compared with conventional erbium-doped fiber glass sensor material, the unleaded fluogermanate glass of erbium and ytterbium codoping of the invention overcomes fluoride chalcogenide glass and silicon (boron) silicate glass as the intrinsic shortcoming of optical sensing material, with work ceiling temperature higher and sensitivity of thermometry, optical fiber can be made and be widely used in heating using microwave field of temperature measurement.
Description
Technical field
The present invention relates to a kind of optical sensing material, more particularly to a kind of unleaded fluorine of High Temperature Optical sensing material erbium and ytterbium codoping
Germanate glass and preparation method thereof, it is adaptable to heating using microwave field of temperature measurement.
Background technology
Heating using microwave with its efficiency high, speed is fast, material generates heat by itself dielectric loss the features such as, be widely used in eating
The fields such as product processing, dry materials, medicine sterilization and family cooking.But due to the presence of strong-electromagnetic field.Make the temperature in microwave field
Degree measurement turns into a technical barrier, causes existing microwave heating equipment mostly to lack effectively and the temperature detecting part of low cost
Part, makes heating using microwave be difficult to temperature control, causes over-heating or underheat phenomenon, influences the effect of heating using microwave.
Because optical fiber electromagnetism interference, small and light are flexible, be suitable for inflammable, explosive, space strictly limit, forceful electric power
Used under the adverse circumstances such as magnetic disturbance.Therefore the optical fiber temperature sensor technology based on fluorescence intensity ratio technology, measures and temperature phase
Two beam intensities launched between the rare earth ion adjacent energy levels of the same sensing material for closing, accuracy is high, cost is relatively low, detection is simple
It is single, using relative ratio, the interference of environment is preferably overcome, considerably improve measurement sensitivity and ceiling temperature.And close
Suitable rear-earth-doped sensing material turns into the key issue of restriction optic temperature sensor.
At present, the optic temperature sensor based on er-doped fluoride and chalcogenide glass material achieves greater advance, but
Due to fluoride, sulfide, physical and chemical performance is poor in itself, and its maximum operating temperature is less than 523K.In recent years, er-doped silicate or boron
Silicate glass also shows that its potentiality as optical temperature sensing material, and its physical and chemical performance is better than fluoride and vulcanization object
System, is expected to improve measurement ceiling temperature, but because its phonon energy is higher, causes up-conversion luminescence efficiency relatively low, measures sensitive
Degree is restricted.Therefore, the suitable er doped silica glasses optical fiber environment-friendly materials of development are needed badly, so as to improve optic temperature sensor constituent element
Operating temperature range and luminous efficiency, it is adaptable to food processing, dry materials, medicine sterilization and the heating using microwave such as family cooking
Field.
The content of the invention
The technical problem to be solved in the present invention is to overcome above-mentioned technical disadvantages, there is provided a kind of High Temperature Optical sensing material erbium
Ytterbium is co-doped with unleaded fluogermanate glass and preparation method thereof.
The fluogermanate formation of glass sheets advantage of germanate and fluoride glass, with moderate phonon energy and into glass
Performance is good, it is easy to prepare, and adds ytterbium ion, erbium ytterbium ion to be realized in fluogermanate glass highly doped, can further improve
Pump energy utilization rate and luminous efficiency, are capable of achieving highly sensitive TEMP in shorter optical fiber, improve temperature
The practicality of sensor.Compared with conventional erbium-doped fiber glass sensor material, this kind of material overcomes fluoride sulfide glass
Glass (poor heat endurance, heat sensing work ceiling temperature it is low) and silicon (boron) silicate glass (phonon energy higher, it is low light
Efficiency, low sensitivity of thermometry) as the intrinsic shortcoming of optical sensing material, for optic temperature sensor provides a kind of suitable
Host material.
The unleaded fluogermanate glass of erbium and ytterbium codoping
Specific technical solution of the invention is as follows：
A kind of unleaded fluogermanate glass of High Temperature Optical sensing material erbium and ytterbium codoping, by mole meter, consisting of：
Wherein, R is the combination of Ga elements and at least one of two kinds of elements of Y, Gd；
It is preferred that described R2O3Middle Ga2O3Material rate is accounted for, by mole being calculated as 6~16.
It is preferred that the R is Ga:Y:Gd=6:5:4 (mol ratios).
Illustrate the effect of each composition below, and above-mentioned compositing range it is preferred the reasons why.
GeO2It is the important necessary composition for forming body as glass network structure and playing a role.In order to ensure glass
Physical and chemical stability, make GeO2Content be higher than 46%.On the other hand, GeO2During too high levels, glass melting temperature liter first
Height, preparing difficulty increases, and the total amount additionally, due to other compositions is very few, and glass is unstable, is unfavorable for actual preparation large scale germanium
, easily there is large stretch of flakes crystallization, GeO in silicate glass2Content should be less than equal to 54%.
R2O3Wherein R represents Ga, the combination with least one of Y or Gd, and this type oxide has refraction high in itself
Rate, can keep the low dispersivity of glass, improve refractive index.The introducing of Ga, Gd and Y reduces the reflection loss of glass, is conducive to
Absorption of the reinforcing material to pump light, improves pumping efficiency.By introducing Ga, the combination with least one of Y or Gd, glass
The heat endurance parameter difference of glass transformation temperature (initial recrystallization temperature with) improve so that glass is in fiber drawing process
With opereating specification wider, the difficulty of devitrification of glass is increased, be conducive to drawing optical fiber.And it is many by introducing Ga, Y and Gd
Composition and turn into the effect that multicomponent glass improves stability, but the importing that the composition should not be excessive.It is excessive to introduce, cause glass
Glass component cannot be completely melt, glass is unstable and crystallization.
The effect of Ba ions is mainly raising stability, glass, improves glass hard (HRC65Yi Shang) and refractive index, but excessive introducing
The balance with other compositions can be destroyed, therefore introduces the Ba ions of 10~20mol%.
The effect of Li ions mainly reduces the viscosity of glass, glass transformation temperature, such that glass is more prone to manufacture, but
It is that excessive introducing can cause the stability of glass to reduce.And in alkali metal, the effect that lithium ion improves stability is maximum, excessively
The introducing of species alkali metal is unfavorable for the stability of glass, therefore only selection introduces the lithium ion of 10~20mol%.
R3+, Ba2+, Li+And rare earth ion is introduced using fluoride form, the mainly presence of fluorine ion can be further
The glass melting temperature of glass is reduced, the preparation of glass is so more beneficial for.On the other hand, the introducing of fluoride, can reduce glass
Phonon energy, improve rare earth ion visible waveband luminous efficiency.
Er ions as light emitting ionic, due to Er ions2H11/2With4S3/2The level spacing of energy level is moderate, belongs to hot coupling
Energy level is closed, when temperature is improved,4S3/2Particle on energy level is conducive to being excited to2H11/2Energy level,2H11/2With4S3/2Two energy levels
Fluorescence intensity uses I respectivelyHWith ISRepresent, then its ratio meets following relation
Wherein, C is constant, and k is Boltzmann constant, and T is temperature, and Δ E is2H11/2With4S3/2The energy gap of two energy levels is big
It is small.
Logarithmic form is deformed to above formula
Carry out the sensitivity (S) that differential can obtain optical temperature sensing again to above formula
After Rare Earth Y b ions are introduced, can further improve erbium ion using pump energy and luminous efficiency, and erbium ytterbium from
Son can be realized in fluogermanate glass it is highly doped, then in shorter optical fiber i.e. be capable of achieving highly sensitive TEMP, carry
The practicality of temperature sensor high.
For fluogermanate glass, the performance such as selected oxide and fluoride refractive index, temperature refraction rate coefficient
The contribution of parameter is different, and oxide is positive temperature refraction rate coefficient, and fluoride is negative temperature specific refractivity.Fluoride excess
The change except glass physicochemistry property can be caused is introduced, a large amount of volatilizations due to fluorine in preparation process can corrode crucible,
Striped is produced, is unfavorable for that optical fiber chemical industry is produced.The fluoride of fluogermanate glass is adjusted by above-mentioned composition design and optimization
And oxide content, so that controllable preparation goes out the fluogermanate glass optical fiber material of the extremely low stabilization of optics distortion factor.
The preparation method of described erbium and ytterbium codoping fluogermanate crown glass, comprises the following steps：
1. the component is well mixed to obtain compound, is put into the platinum crucible added a cover, crucible is placed in Elema electricity
In stove, heated up with stove, setting heating rate is 25K/min, when furnace temperature reaches 1300-1400 DEG C, continue to found 40-50 minutes
To the glass metal of melting, high purity oxygen gas water removal is passed through in melting process always；
2. by the homogenized clarification of glass metal after water removal, then Quick pouring is to being pre-heated on 500-520 DEG C of mould,
It is put into and has warmed up into the Muffle furnace of 530-560 DEG C of the glass transition temperature of the glass metal, after being incubated 2-3 hours, then with
9-11 DEG C/h of speed is cooled to 90-100 DEG C, is then shut off Muffle furnace, is cooled to room temperature.
Beneficial effect：
(1) the unleaded fluogermanate glass of erbium and ytterbium codoping has good chemical stability and high-temperature stability, and it is used as light
Temperature sensing material is learned, between 293K-750K, the work ceiling temperature of the material is better than general glass to working range.
(2) the unleaded fluogermanate glass of erbium and ytterbium codoping is sensitive with optical sensitivity high as optical temperature sensing material
Degree can reach 0.0024K-1, it is minimum to can reach 0.0017K-1。
(3) material mixed compared to erbium list, because ytterbium ion can absorb more pump energies, by ytterbium (Yb)2F5/2Pump energy effectively can be passed to erbium (Er) ion by energy level4I11/2Energy level, further improves the upload of erbium ion
Light efficiency is changed, is conducive to improving its sensitivity as optical sensing material.
(4) erbium and ytterbium codoping unleaded fluogermanate glass is free of poisonous lead as harmful matter, it is to avoid to the mankind and the danger of environment
Evil, is a kind of new type high temperature optical sensing material for having very much a market potential.
(5) manufacture craft of the unleaded fluogermanate glass of erbium and ytterbium codoping of the invention is simple, and production cost is relatively low.Can profit
The optical fiber with excellent up-conversion luminescence performance is directly drawn into the unleaded fluogermanate glass preform of erbium and ytterbium codoping.Using erbium
Ytterbium is co-doped with the short glass optical fiber of unleaded fluogermanate as temperature sensor probe material, and intensity is high, good toughness, High-Voltage Insulation, resists
Electromagnetic interference, therefore the temperature rise variation tendency of joint can be in time grasped, the accurate temperature regime for judging external environment condition, and light
Fibre probe is compact and flexible, it is easy to installs and safeguards.
Brief description of the drawings
Fig. 1 is the Raman spectrogram of embodiment 1.
Fig. 2 be embodiment 1 980nm wavelength it is laser diode-pumped under, in 300-750K temperature ranges test
The up-conversion fluorescence spectrum of 500-600nm erbiums.■ is the fluorescence with temperature of optical temperature sensing material under conditions of 300K in figure
Variation relation curve, ● be the variation relation curve of the fluorescence with temperature of optical temperature sensing material under conditions of 350K, ▲
It is the variation relation curve of the fluorescence with temperature of optical temperature sensing material under conditions of 400K, ▼ is optics under conditions of 450K
The variation relation curve of the fluorescence with temperature of temperature sensing material, ◆ it is the fluorescence of optical temperature sensing material under conditions of 500K
Variation with temperature relation curve,For the variation relation of the fluorescence with temperature of optical temperature sensing material under conditions of 550K is bent
Line,It is the variation relation curve of the fluorescence with temperature of optical temperature sensing material under conditions of 600K,It is the condition of 650K
The variation relation curve of the fluorescence with temperature of lower optical temperature sensing material, ★ is optical temperature sensing material under conditions of 700K
Fluorescence with temperature variation relation curve,It is the change of the fluorescence with temperature of optical temperature sensing material under conditions of 750K
Relation curve,
Fig. 3 is the graph of a relation of the gained temperature control curve of embodiment 1 and temperature.
Specific embodiment
Table 1：
Embodiment 1：
According to the formula of table 1, the weight of corresponding each component is calculated, weigh each raw material and be well mixed；Set and heat up
Speed is 25K/min, compound is put into the platinum crucible added a cover to be warming up to stove in 1300 DEG C of Elema electric furnace and melted
The glass metal for being melted for 40 minutes, being passed through high purity oxygen gas (purity is higher than 99.995%) all the time in glass melting process is carried out
Atmosphere protection is removing the moisture in glass metal.After the dewatered homogenized clarification of glass metal, Quick pouring is to being pre-heated to
In 500 DEG C of mould, then it is put into rapidly and has warmed up into 540 DEG C of Muffle furnace, is incubated 2 hours；Again with 10 DEG C/h of speed
Muffle furnace is down to 90 DEG C by rate, is then shut off Muffle furnace, is cooled to room temperature, the unleaded fluogermanate of the erbium and ytterbium codoping after being annealed
Glass.
The unleaded fluogermanate glass processing of erbium and ytterbium codoping after annealing into 10 × 20 × 1 millimeter sheet glass and polish use
In spectrum test.Moderate glass phonon energy can effectively facilitate rare earth ion up-conversion luminescence.Tested by Raman spectrum, such as
Shown in Fig. 1, the maximum phonon energy of embodiment 1 in 900 wave numbers or so, less than silicate glass and quartz glass (about 1100 ripples
Number), the matrix is conducive to obtaining efficient up-conversion luminescence, it is not necessary to high power laser pumping, reduces the cost of sensor.
Under the pumping of 980nm semiconductor laser 300mW power, it is tested in 300-750K temperature ranges, 500-600nm ripples
The up-conversion fluorescence spectrum of section erbium.As shown in Figure 2, the present embodiment gained unleaded fluogermanate glass of erbium and ytterbium codoping obtains center
Wavelength is in the luminous of 528nm and 546nm.According to the up-conversion fluorescence spectrum for measuring, calculate 528nm under different temperatures with
The fluorescence intensity ratio (R=I528/I546) of 546nm.Fluorescence intensity ratio meets with ShiShimonoseki with the sensitivity (S) of optical temperature sensing
System
The optical temperature sensing sensitivity based on embodiment 1 that Fig. 3 is given in the range of 300-750K is corresponding with temperature
Relation curve, the material temperature sensing sensitivity can reach 0.0022K-1, minimum 0.0018K-1, can be used as high temperature light
Learn temperature sensing material.
Embodiment 2：
According to the formula of table 1, the weight of corresponding each component is calculated, weigh each raw material and be well mixed；Set and heat up
Speed is 25K/min, compound is put into the platinum crucible added a cover to be warming up to stove in 1400 DEG C of Elema electric furnace and melted
The glass metal for being melted for 50 minutes, in glass melting process being passed through high purity oxygen gas all the time carries out atmosphere protection to remove glass
Moisture in liquid.After the dewatered homogenized clarification of glass metal, Quick pouring to being pre-heated in 520 DEG C of mould, then
Rapid being put into is had warmed up into 550 DEG C of Muffle furnace, is incubated 3 hours, then be down to 90 DEG C, Ran Houguan with 11 DEG C/h of speed
Muffle furnace is closed, room temperature is cooled to, the unleaded fluogermanate glass of the erbium and ytterbium codoping after being annealed.
The unleaded fluogermanate glass transparent of erbium and ytterbium codoping that the present embodiment is prepared, by the glass processing after annealing into 10
× 20 × 1 millimeter of sheet glass is simultaneously polished, and under 980nm diode-end-pumpeds, tests it in 300-750K temperature models
In enclosing, the up-conversion fluorescence spectrum of 500-600nm wave band erbiums.By the result of up-conversion fluorescence spectrum, different temperatures is calculated
Under 528nm and 546nm fluorescence intensity ratio, sensitivity (S) relational expression sensed using fluorescence intensity ratio and optical temperature is real
Example 3 is applied in 300-750K temperature ranges, optical sensitivity scope is in 0.0019-0.0021K-1, can be sensed as optical temperature
Material.Restriction is added in technical scheme on heating rate, whether suitable asks ten thousand teachers to see.
Embodiment 3：
According to the formula of table 1, the weight of corresponding each component is calculated, weigh each raw material and be well mixed；Set and heat up
Speed is 25K/min, compound is put into the platinum crucible added a cover to be warming up to stove in 1350 DEG C of Elema electric furnace and melted
The glass metal for being melted for 45 minutes, in glass melting process being passed through high purity oxygen gas all the time carries out atmosphere protection to remove glass
Moisture in liquid.After the dewatered homogenized clarification of glass metal, Quick pouring to being pre-heated in 510 DEG C of mould, then
Rapid being put into is had warmed up into 545 DEG C of Muffle furnace, is incubated 2.5 hours, then is down to 95 DEG C with 10 DEG C/h of speed, then
Muffle furnace is closed, room temperature is cooled to, the unleaded fluogermanate glass of the erbium and ytterbium codoping after being annealed.
The unleaded fluogermanate glass transparent of erbium and ytterbium codoping that the present embodiment is prepared, by the glass processing after annealing into 10
× 20 × 1 millimeter of sheet glass is simultaneously polished, and under 980nm diode-end-pumpeds, tests it in 300-750K temperature models
In enclosing, the up-conversion fluorescence spectrum of 500-600nm wave band erbiums.By up-conversion fluorescence spectrum, calculate under different temperatures
The fluorescence intensity ratio of 528nm and 546nm, sensitivity (S) relational expression sensed using fluorescence intensity ratio and optical temperature, embodiment
3 in 300-750K temperature ranges, and optical sensitivity scope is in 0.0019-0.0021K-1, can be used as optical temperature sensing material.
Embodiment 4：
According to the formula of table 1, the weight of corresponding each component is calculated, weigh each raw material and be well mixed；Set and heat up
Speed is 25K/min, compound is put into the platinum crucible added a cover to be warming up to stove in 1380 DEG C of Elema electric furnace and melted
The glass metal for being melted for 48 minutes, in glass melting process being passed through high purity oxygen gas all the time carries out atmosphere protection to remove glass
Moisture in liquid.After the dewatered homogenized clarification of glass metal, Quick pouring to being pre-heated in 515 DEG C of mould, then
Rapid being put into is had warmed up into 560 DEG C of Muffle furnace, is incubated 3 hours, then be down to 95 DEG C, Ran Houguan with 11 DEG C/h of speed
Muffle furnace is closed, room temperature is cooled to, the unleaded fluogermanate glass of the erbium and ytterbium codoping after being annealed.
The unleaded fluogermanate glass transparent of erbium and ytterbium codoping that the present embodiment is prepared, by the glass processing after annealing into 10
× 20 × 1 millimeter of sheet glass is simultaneously polished, and under 980nm diode-end-pumpeds, tests it in 300-750K temperature models
In enclosing, the up-conversion fluorescence spectrum of 500-600nm wave band erbiums.By up-conversion fluorescence spectrum, calculate under different temperatures
The fluorescence intensity ratio of 528nm and 546nm, sensitivity (S) relational expression sensed using fluorescence intensity ratio and optical temperature, embodiment
4 in 300-750K temperature ranges, and optical sensitivity scope is in 0.0018-0.0023K-1, can be used as optical temperature sensing material.
Embodiment 5：
According to the formula of table 1, the weight of corresponding each component is calculated, weigh each raw material and be well mixed；Set and heat up
Speed is 25K/min, compound is put into the platinum crucible added a cover to be warming up to stove in 1310 DEG C of Elema electric furnace and melted
The glass metal for being melted for 42 minutes, in glass melting process being passed through high purity oxygen gas all the time carries out atmosphere protection to remove glass
Moisture in liquid.After the dewatered homogenized clarification of glass metal, Quick pouring to being pre-heated in 505 DEG C of mould, then
Rapid being put into is had warmed up into 530 DEG C of Muffle furnace, is incubated 2.2 hours, then is down to 90 DEG C with 10 DEG C/h of speed, then
Muffle furnace is closed, room temperature is cooled to, the unleaded fluogermanate glass of the erbium and ytterbium codoping after being annealed.
The unleaded fluogermanate glass transparent of erbium and ytterbium codoping that the present embodiment is prepared, by the glass processing after annealing into 10
× 20 × 1 millimeter of sheet glass is simultaneously polished, and under 980nm diode-end-pumpeds, tests it in 300-750K temperature models
In enclosing, the up-conversion fluorescence spectrum of 500-600nm wave band erbiums.By up-conversion fluorescence spectrum, calculate under different temperatures
The fluorescence intensity ratio of 528nm and 546nm, sensitivity (S) relational expression sensed using fluorescence intensity ratio and optical temperature, embodiment
5 in 300-750K temperature ranges, and optical sensitivity scope is in 0.0017-0.0024K-1, can be used as optical temperature sensing material.
Embodiment 6：
According to the formula of table 1, the weight of corresponding each component is calculated, weigh each raw material and be well mixed；Set and heat up
Speed is 25K/min, compound is put into the platinum crucible added a cover to be warming up to stove in 1350 DEG C of Elema electric furnace and melted
The glass metal for being melted for 45 minutes, in glass melting process being passed through high purity oxygen gas all the time carries out atmosphere protection to remove glass
Moisture in liquid.After the dewatered homogenized clarification of glass metal, Quick pouring to being pre-heated in 515 DEG C of mould, then
Rapid being put into is had warmed up into 535 DEG C of Muffle furnace, is incubated 2.5 hours, then is down to 90 DEG C with 10 DEG C/h of speed, then
Muffle furnace is closed, room temperature is cooled to, the unleaded fluogermanate glass of the erbium and ytterbium codoping after being annealed.
The unleaded fluogermanate glass transparent of erbium and ytterbium codoping that the present embodiment is prepared, by the glass processing after annealing into 10
× 20 × 1 millimeter of sheet glass is simultaneously polished, and under 980nm diode-end-pumpeds, tests it in 300-750K temperature models
In enclosing, the up-conversion fluorescence spectrum of 500-600nm wave band erbiums.By up-conversion fluorescence spectrum, calculate under different temperatures
The fluorescence intensity ratio of 528nm and 546nm, sensitivity (S) relational expression sensed using fluorescence intensity ratio and optical temperature, embodiment
6 in 300-750K temperature ranges, and optical sensitivity scope is in 0.0017-0.0021K-1, can be used as optical temperature sensing material.
The unleaded fluogermanate glass of erbium and ytterbium codoping prepared by the present invention, glass transparent, phonon energy is moderate,
In 293K-750K temperature ranges, up-conversion luminescence is strong, and optical sensitivity model is in 0.0017K-1-0.0024K-1Between, with height
Sensitivity, high workload ceiling temperature can be used as new type high temperature optical sensing material.
Claims (5)
1. the unleaded fluogermanate glass of a kind of High Temperature Optical sensing material erbium and ytterbium codoping, it is characterised in that by mole meter,
Including the following raw material：
Wherein, R is the combination of Ga elements and at least one of the element of Y, Gd two.
2. the unleaded fluogermanate glass of High Temperature Optical sensing material erbium and ytterbium codoping according to claim 1, it is characterised in that
Described R2O3Middle Ga2O3Material rate is accounted for, by mole being calculated as 6~16.
3. the unleaded fluogermanate glass of High Temperature Optical sensing material erbium and ytterbium codoping according to claim 1, it is characterised in that
Described R2O3Middle R is combined for Ga, Y, Gd three, and mol ratio is Ga:Y:Gd=6:5:4.
4. the preparation method of the unleaded fluogermanate glass of a kind of High Temperature Optical sensing material erbium and ytterbium codoping, it is characterised in that including
Following steps：
1. raw material components as claimed in claim 1 are well mixed to obtain compound, are put into the platinum crucible added a cover, crucible is put
In Elema electric furnace, heated up with stove, setting heating rate is 25K/min, when furnace temperature reaches 1300-1400 DEG C, continues to found
The glass metal for being melted for 40-50 minutes, is passed through high purity oxygen gas water removal always in melting process；
2. by the homogenized clarification of glass metal after water removal, then Quick pouring is put into being pre-heated on 500-520 DEG C of mould
Have warmed up into the Muffle furnace of 530-560 DEG C of the glass transition temperature of the glass metal, after being incubated 2-3 hours, then with 9-11
DEG C/h speed be cooled to 90-100 DEG C, be then shut off Muffle furnace, be cooled to room temperature, obtain the unleaded fluogermanic acid of erbium and ytterbium codoping
Salt glass.
5. the unleaded fluogermanate glass of High Temperature Optical sensing material erbium and ytterbium codoping as claimed in claim 1 or 2 is used for optical fiber.
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| CN201611115573.4A CN106746621B (en) | 2016-12-07 | 2016-12-07 | erbium-ytterbium co-doped lead-free fluorine germanate glass of high-temperature optical sensing material and preparation method thereof |
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Cited By (1)
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| CN112410032A (en) * | 2020-11-20 | 2021-02-26 | 浙江大学 | Erbium silicate for realizing sensitized luminescence based on energy transfer among particles and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54127911A (en) * | 1978-03-29 | 1979-10-04 | Fujitsu Ltd | Optical glass |
| CN102211873A (en) * | 2011-03-23 | 2011-10-12 | 中国科学院上海光学精密机械研究所 | 3-micron luminescent rare earth ion-doped fluorogermanate laser glass and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54127911A (en) * | 1978-03-29 | 1979-10-04 | Fujitsu Ltd | Optical glass |
| CN102211873A (en) * | 2011-03-23 | 2011-10-12 | 中国科学院上海光学精密机械研究所 | 3-micron luminescent rare earth ion-doped fluorogermanate laser glass and preparation method thereof |
Non-Patent Citations (1)
| Title |
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| 赵连城、国凤云: "《信息功能材料学》", 31 July 2005 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112410032A (en) * | 2020-11-20 | 2021-02-26 | 浙江大学 | Erbium silicate for realizing sensitized luminescence based on energy transfer among particles and preparation method thereof |
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